N-Thio- and N-selenophenacylamidines: electrophilic activation as a route to some 1-hetero-3-aza-4-dimethylaminobuta-1,3-dienes

Abstract

The preparation of 2-phenyl-4-dimethylamino-1-aza-, 1-oxa-, 1-thia-, 1-selena-3-azabuta-1,3-dienes as well as their 4-methyl derivatives is described following a new heteroatom interchange reaction process. Heteronucleophilic attack at one particular reactive site of bis-electrophilic amidinium salts is the key feature of the process. In addition, we also disclose that the substituted 1-oxa-3-aza- and 1,3-diazabuta-1,3-dienes can be obtained by a reactional transformation cascade initiated by either silver acetate addition or tosyl azide [3+2] cycloaddition onto the CS or CSe double bonds of the 1-thia- and 1-selena-3-azabuta-1,3-diene analogues.

References

1. (a) D. L. Boger and S. M. Weinreb, in Hetero Diels–Alder Methodology in Organic Synthesis, ed. H. H. Wasserman, Academic Press, San Diego, 1987; (b) W. Carruthers, in Cycloaddition Reactions in Organic Synthesis, ed. J. E. Baldwin and P. D. Magnus, Pergamon Press, Oxford, 1990, vol. 8; (c) D. L. Boger, in Comprehensive Organic Synthesis, ed. L. A. Paquette, Pergamon Press, Oxford, 1991, vol. 5, p. 451; (d) H. Waldmann, Synthesis, 1994, 535; (e) L. Tietze and G. Kettschau, Top. Curr. Chem., 1997, 189, 1.
2. (a) J. C. Meslin and H. Quiniou, Bull. Soc. Chim. Fr., 1979, 116, 347; (b) J. C. Rozé, J. P. Pradère, G. Duguay, A. Guevel, C. G. Tea and H. Quiniou, Sulfur Lett., 1983, 1, 115; (c) C. G. Tea, J. P. Pradère and H. Quiniou, J. Org. Chem., 1985, 50, 1545; (d) J. P. Pradère, J. C. Rozé, H. Quiniou, R. Danion-Bougot, D. Danion and L. Toupet, Can. J. Chem., 1986, 64, 597; (e) C. Cellerin, C. G. Tea, J. P. Pradère, A. Guingant and P. Guenot, Sulfur Lett., 1988, 8, 205; (f) J. P. Pradère, F. Tonnard, A. Abouelda, C. Cellerin, M. Andriamanamihaja, B. Jousseaume, L. Toupet and P. Guénot, Bull. Soc. Chim. Fr., 1993, 130, 610; (g) D. Dubreuil, J. P. Pradère, N. Giraudeau, M. Goli and F. Tonnard, Tetrahedron Lett., 1995, 36, 237; (h) F. Purseigle, D. Dubreuil, A. Marchand, J. P. Pradère, M. Goli and L. Toupet, Tetrahedron, 1998, 54, 2545.
3. A. Marchand, D. Mauger, A. Guingant and J. P. Pradère, Tetrahedron: Asymmetry, 1995, 6, 853.
4. (a) J. Liebscher, M. Pätzel and Y. F. Kelboro, Synthesis, 1989, 672; (b) C. Cellerin, J. P. Pradère, D. Danion and F. Tonnard, C. R. Acad. Sci. Paris, 1991, 313, Série II, 517; (c) A. Rolfs and J. Liebscher, J. Org. Chem., 1997, 62, 3480.
5. For a preliminary study about the heteroatom interconversion reaction concept as shown in Scheme 1 see reference 4a. See also for related work: (a) H. G. Gold, Angew. Chem., 1960, 72, 956; (b) J. Liebscher and H. Hartmann, Synthesis, 1976, 403.
6. J. C. Meslin, A. Reliquet, F. Reliquet and C. G. Tea, C. R. Acad. Sci. Paris, 1978, 286, Série C, 397.
7. (a) Semi empirical PM3 calculations were carried out with SPARTAN software (4.0 version) on a Silicon Graphics Indy. For PM3 calculations see: J. J. P. Stewart, Comput. Chem., 1989, 42, 12; (b) F. Purseigle,PhD Thesis (30/01/97), University of Nantes.
8. J. Liebscher, Synthesis, 1988, 655.
9. For a recent review on conversion of the thiocarbonyl group into the carbonyl group, see: A. Corsaro and V. Pistarà, Tetrahedron, 1998, 54, 15027.
10. M. Avalos, R. Babiano, C. J. Duran, J. L. Jiménez and J. C. Palacios, Tetrahedron Lett., 1994, 35, 477.
11. J. Barluenga and M. Thomas, in Advances in Heterocyclic Chemistry, ed. A. R. Katritzky, Academic Press, San Diego, 1993, vol. 57, p. 61.
12. H. Schaumann, in The chemistry of double-bonded functional groups, ed. S. Patai Interscience Publication, John Wiley and Sons, New York, 1989, vol. 2, ch. 17, p. 1338.
13. Selected torsion angles: N1–C2–N3–C4 equal to –153.76°c in 6a and 123.47°c in 6b; C2–N3–C4–N2 equal to –170.83°c in 6a and 166.54°c in 6b.
14. C. K. Johnson, ORTEP Report ORNL-3794, Oak Ridge National Laboratory, Tenessee, USA, 1965.
15. S. N. Mazumdar and M. P. Mahajan, Synthesis, 1990, 417.
16. (a) P. Luthardt and E. U. Würthwein, Tetrahedron Lett., 1988, 29, 921; (b) S. N. Mazumdar and M. P. Mahajan, Tetrahedron, 1991, 47, 1473; (c) S. N. Mazumdar, S. Mukherjee, A. Z. Sharma, D. Sengupta and M. P. Mahajan, Tetrahedron, 1994, 50, 7579; (d) P. D. Dey, A. K. Sharma, P. V. Bharatam and M. P. Mahajan, Tetrahedron, 1997, 53, 13829; (e) A. K. Sharma and M. P. Mahajan, Tetrahedron, 1997, 53, 13841.
17. (a) K. Burger, E. Huber, N. Sewald and H. Partscht, Chem. Ztg., 1986, 110, 83; (b) W. M. F. Fabian and G. Kollenz, J. Phys. Org. Chem., 1994, 7, 1; (c) E. Rossi, G. Abbiati and E. Pini, Tetrahedron, 1997, 53, 14107.
18. For dipolarophilic properties of 1 see: R. Danion-Bougot, R. Tuloup, D. Danion, J. P. Pradegrave;re and F. Tonnard, Sulfur Lett., 1989, 9, 245.
19. C. K. Fair, MolEN. An Interactive Intelligent System for Crystal Structure Analysis, Enraf-Nonius, Delft, The Netherlands, 1990.
20. A. L. Spek, HELENA. Program for the handling of CAD4-Diffractomer output SHELX(S/L), 1997, Utrecht University, Utrecht, The Netherlands.
21. A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori and R. Spagna, J. Appl. Crystallogr., 1998, 31, 74.
22. G. M. Sheldrick, SHELX93. Program for the renement of crystal structures, 1993, University of Göttingen, Germany.
23. International tables for X-ray crystallography, Kynoch Press(present distributor D. Reidel, Dordrecht), Birmingham, 1974, vol. IV.
24. A. L Spek, PLATON. A multipose crystallographic tool, 1998, Utrecht University, Utrecht, The Netherlands.
25. G. Häfelinger, in The chemistry of amidines and imidates, ed. S. Patai, Interscience Publication, John Wiley and Sons, New York, 1975, ch. 1, p. 53.
26. A. J. Blake, H. McNab and M. E. Ann Murray, J. Chem. Soc., Perkin Trans. 1, 1989, 589.
27. M. Regitz, J. Hocker and A. Liedhegener, Organic Syntheses, ed. J. Wiley and Sons, New York, 1988, Coll. Vol. V, p. 179.
28. B. Seiller, D. Heins, C. Bruneau and P. H. Dixneuf, Tetrahedron, 1995, 51, 10901.